Polyglycidyl esters

ABSTRACT

POLYGLYCIDYL ESTERS OF FORMULA   (OXIRANYL-CH2-OOC)M-R1-COO-A-OOC-R4-(COO-CH2-   CH&lt;(-CH2-O-))N   WHEREIN R1 AND R2 INDEPENDENTLY OF EACH OTHER DENOTES A RESIDUE, OBTAINED BY REMOVAL OF THE CARBOXYL GROUPS, OR AN ALIPHATIC OR CYCLOALIPHATIC POLYCARBOXYLIC ACID HAVING 2 TO 4 CARBOXYL GROUPS, A REPRESENTS THE RESIDUE, OBTAINED BY REMOVAL OF THE TWO HYDROXYL GROUPS, OF A POLYALKYLENE GLYCOL OF AVERAGE MOLECULAR WEIGHT OF AT LEAST 200, AND WHEREIN M AND N DENOTE INTEGERS HAVING A VALUE OF AT LEAST 1 AND AT MOST 3, PREFERABLY 1 OR 2.

United States Patent Oflice Patented Mar. 21 1972 U.S. Cl. 260-348 A 11 Claims ABSTRACT OF THE DISCLOSURE Polyglycidyl esters of formula TI IT o till ti ii [iii wherein R and R independently of each other denotes a residue, obtained by removal of the carboxyl groups, or an aliphatic or cycloaliphatic polycarboxylic acid having 2 to 4 carboxyl groups, A represents the residue, ob tained by removal of the two hydroxyl groups, of a polyalkylene glycol of average molecular weight of at least 200, and wherein m and n denote integers having a value of at least 1 and at most 3, preferably 1 or 2.

The subject of the present invention is new long-chain polyglycidyl esters containing aliphatic or cycloaliphatic acid residues, of general formula wherein R and R independently of each another denote a residue, obtained by removal of the carboxyl groups, of an aliphatic or cycloaliphatic polycarboxylic acid having 2 to 4 carboxyl groups, A represents the residue, obtained by removal of the two hydroxyl groups, of a polyalkylene glycol of average molecular weight of at least 200, and wherein m and n denote integers having a value of at least 1 and at most 3, preferably 1 or 2.

Amongst the polyglycidyl esters according to the invention, of Formula I, the symmetrical compounds in which R =R and 'm'=n can be most easily manufactured. Furthermore such polyglycidyl esters, in which R and R denote the residue of a mononuclear cycloaliphatic polycarboxylic acid or of an aliphatic polycarboxylic acid having 2 or 3 carboxyl groups and in which the residue A is derived from a polyalkylene glycol which is built up of alkylene glycol units having 2 to 6 carbon atoms are, in addition to being distinguished by easy accessibility, also distinguished by particularly valuable technical properties.

Particularly preferred compounds are the symmetrical diglycidyl esters of formula A denotes the residue, obtained by removal of the two hydroxyl groups, of a polyalkylene glycol of formula wherein Alkylene is an alkylene residue having 2 to 6 carbon atoms and the number x is so chosen that the A lkylene- H IT LU;

average molecular weight of the polyalkylene glycol is a least 200, preferably 250 to 2500.

The polyglycidyl esters according to the invention are as a rule liquid at room temperature. The compounds derived from polyalkylene glycols having higher glycol structural units such as for example polyhexanediol are mostly solid and crystalline.

The new polyglycidyl esters of Formula I can be manufactured by reacting a partial ester of formula wherein R R A, m and n have the same significance as in Formula I and Cat denotes a cation, preferably hydrogen or alkali metal, in a single stage or several stages, with an epihalogenohydrin or B-methylepihalogenohydrin with elimination of Cat-Hal, denotes the halogen atom of the epihalogenohydrin or B-methylepihalogenohydrin, in a manner which is in itself known. It is for example possible to proceed by reacting alkali salts of the partial esters, such as for example the di-sodium salt of the half-ester from 1 mol of a polypropylene glycol of molecular weight 425 and 2 mols of hexahydrophthalic anhydride at elevated temperature with an excess of the epihalogenohydrin or B-methylepihalogenohydrin such as epichlorhydrin or fi-methylepichlorhydrin, filtering off the inorganic salt which has separated out and distilling off the excess epichlorhydrin.

It is furthermore possible to react the partial ester in the form of the free acid with an excess of epihalogenohydrin, that is to say as a rule in an amount of more than 2 mols per free carboxyl group, in the presence of suitable catalysts such as for example tertiary amines quaternary ammonium salts or ion exchanger resins, in a single stage to give the glycidyl ester. In this reaction the corresponding halogenohydrin ester first forms, with the epihalogenohydrin adding to the free carboxyl groups of the half-ester. The excess epihalogenohydrin then eliminates hydrogen halide from the halogenohydrin ester groups with the formation of glycidyl ester groups and of an equivalent quantity of glycerine dihalogenohydrin. The latter is distilled off after the completion of the reaction, together with epihalogenohydrin, and can be regenerated by treatment with strong alkalis to give the epihalogenohydrin. Such a single-stage catalytic process is for example described in German patent specification 1,165,030. The process sufi'ers from the disadvantage of yielding relatively impure products which, as a result of major proportions of halogenohydrin esters, possess a relatively low epoxide oxygen content and a high halogen or chlorine content.

The new glycidyl esters according to the invention, of Formula I, are preferably manufactured by reactingan epihalogenohydrin, preferably epichlorhydrin, in the presence of a catalyst such as preferably a tertiary amine or a quaternary ammonium base or a quaternary ammonium salt, with a partial ester of Formula IV and treating the resulting product containing halogenohydrin groups with reagents which remove hydrogen halide.

Suitable catalysts for the addition of epichlorhydrin are above all tertiary amines such as triethylamine, tri-npropylamine, benzyldimethylamine, N,N'-dimethylaniline and triethanolamine; quaternary ammonium bases such as bcnzyltrimethylammonium hydroxide; quaternary ammoiiiumsalts such as tetramcthylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, bcnzyltrimethylammonium acetate, methyltriethylammonium chloride; and furthermore ion exchanger resins having tertiary or quaternary amino groups, and also trialkylhydrazonium salts such as trimethylhydrazonium iodide.

Suitable catalysts are furthermore also low molecular thioesters and sulphonium salts or compounds which can change into thioethers or sulphonium compounds with the epihalogenohydrins, such as hydrogen sulphide, sodium sulphide or mercaptans.

As such thioethers or sulphonium salts there may be mentioned: diethyl sulphide, B-hydroxyethyl ethyl sulphide, fi-hydroxypropyl ethyl sulphide, w-hydroxy-tetramethylene ethyl sulphide, thiodiglycol, mono-B-cyanoethyl thioglycol ether, dibenzyl sulphide, benzyl ethyl sulphide, benzyl butyl sulphide, trimethylsulphonium iodide, tris- (fl-hydroxyethyl)sulphonium chloride, dibenzylmethylsulphonium bromide, 2,3-epoxypropylmethylethylsulphonium iodide, dodecyl methyl sulphide and dithiane.

Strong alkalis such as anhydrous sodium hydroxide or aqueous sodium hydroxide solution are as a rule used for the dehydrohalogenation but it is also possible to employ other alkaline reagents such as potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate or potassium carbonate.

The dehydrohalogenation can in turn be carried out in several stages. Thus it is possible first to treat at elevated temperature with solid sodium or potassium hydroxide and after distilling off the excess epihalogenohydrin to heat in an inert solvent with a less than equivalent amount of concentrated alkali hydroxide solution, for example 50% strength sodium hydroxide solution, as is described in German published specification 1,211,177.

Possible epihalogenohydrins are epibromhydrin and above all epichlorhydrin. Good yields are obtained if an excess of epichlorhydrin, and in particular preferably 5 to 40- mols of epichlorhydrin per carboxyl group, are used. During the first reaction, before the addition of alkali, a partial epoxidation of the bischlorhydrin ester of the partial ester (IV) already takes place. The epichlorhydrin, which acts as a hydrogen chloride acceptor is thereby partially converted to glycerine dichlorohydrin. This is again regenerated to give epichlorhydrin on treatment with alkali.

With this preferred process variant last described excellent results can be obtained especially also in the glycidylation, according to the invention, of the condensation products of 2 mols of an aliphatic or cycloaliphatic polycarboxylic acid anhydride and 1 mol of a long-chain polyalkylene glycol. The procedure developed for this new group of glycidyl esters which confer flexibility is also economically interesting since it is possible to work under very concentrated conditions (solutions of 38-50% of glycidyl compound in the epichlorhydrin) and since the yields are in general good, that is to say amount to between 93% and 99% of theory. The epoxide content of the technical products is then as a rule between 93 and 100% of theory and the chlorine content between and 1.2%.

- Processes for the manufacture of the polyglycidyl esters of partial esters from 1 mol of a low molecular polyalcohol or glycol (molecular weight at most about 150) such. as, ethylene glycol, diethylene glycol or triethylene glycol and n or 2 mols of a dicarboxylic acid anhydride such as phthalic anhydride have already been described separately manufactured in one stage and then converted with epichlorohydrin into the polyglycidyl esters (compare German published specification 1,165,030), or the partial esters are produced on glycidylation in situ by reacting a mixture of epichlorhydrin, dicarboxylic acid anhydride and polyalcohol or polyglycol. These known processes use ion exchangers as addition catalysts, as well as using a very large excess of epichlorhydrin (the solutions contain only 3.56.9% by weight of ester-carboxylic acid in the epichlorhydrin) and for this reason these processes are economically less interesting because of the epichlorhydrin losses which can never be avoided. The technical crude products obtained according to the known processes show high chlorine contents (3l0%) so that theycannot be considered for many technical applications because of the corrosion properties.

The partial esters of Formula ilV used as starting compounds can for example be manufactured according-to known processes by reaction of 2 mols of an aliphatic or cycloaliphatic polycarboxylic acid anhydride with 1 mol of a polyalkylene glycol of formula. v v

" HO-A-OH (v) wherein the symbol A has the same significance as in Formula I and wherein the polyalkylene glycol (V) has an average molecular weight of at least 200, preferably 250-2500.

As suitable aliphatic polycarboxylic acid anhydrides there may be mentioned: succinic anhydride, dodecyl succinic anhydride, adipic acid polyanhydride, sebacic acid polyanhydride; 4-carboxybutane-l,Z-dicarboxylic acid anhydride, maleic anhydride, adducts of maleic anhydride to unsaturated aliphatic hydrocarbons such as dipentene or tetrapropylene.

Suitable cycloaliphatic polycarboxylic acid anhydrides are for example: hexahydrophthalic anhydride, 4-methyl-" hexahydrophthalic anhydride, A -tetrahydrophthalic anhydride, 4-methyl-A tetrahydrophthalic anhydride and the isomer mixtures obtained by isomerisation of tetrahydrophthalic anhydride in the presence of suitable catalysts such as metallic palladium or ruthenium (compare U.S. Pat. specification 2,764,597), which contain 4-methy1-A -tetrahydrophthalic anhydride, 4 methyl A tetrahydrophthalic anhydride and 4-mcthyl A tetrahydrophthalic anhydride as the main components; furthermore,- cyclic 1:1 adducts of maleic anhydride to compounds such -as cyclopentadiene (:uadicanhydride), methylcyclopem tadiene (=methylnadicanhydride), hexachlorocyclopentadiene (:chlorendicanhydride), natural or isomerised un-" saturated fatty acids such as oleic acid, linseed oil fatty acid (=Admerginate acid), anthracene, fl-naphthol and others.

Possible polyalkylene glycols of Formula V are above all the polyethylene glycols, polypropylene glycols, polybutylene glycols or polyhexanediols having an average molecular weight of at least 200, and prefarably molecular weights of about 250 to about 2500.

The new polyglycidyl esters, according to the invention, of Formula I react with the usual curing agents for epoxide compounds and can therefore be cross-linked or cured by adding such curing agents, analogously to other polyfunctional epoxide compounds or epoxide resins. Possible curing agents of this kind are basic or acid compounds.

The curing properties of the polyglycidyl esters (I) can vary depending on the acid strength of the polycarboxylic' acid incorporated. Derivatives of strong dicarboxylic acids -value less than 4) as a rule already cure completely in the cold with amine curing agents whilst derivatives of weaker polycarboxylic acids as a rule can only be cured by 'warming.

As suita ble curing agents there may for example be mentioned: amines or amides such as aliphatic, cycloaliphatic or aromatic, primary, secondary and tertiary amines, for example monoethanolamine, ethylene diamine, hexamethylene diamine, trimethylhexamethylene diamine,

diethylene triamine, triethylene tetramine, tetraethylene pentamine, N,N-dimethylpropylene diamine-1,3, N,N-diethylpropylene diamine-l,3, 2,2-bis(4'-aminocyclohexyl) propane, 3,5,5-trimethyl-3-(-aminomethyl) cyclohexylamine (isophorone diamine), Mannich bases such as 2,4,6-tris(dimethylaminomethyl)phenol; m-phenylene diamine, p-phenylene diamine, bis(4-aminophenyl)-methane, bis(4-aminophenyl)sulphone and m-xylylene diamine; adducts of acrylonitrile or monoepoxides such as ethylene oxide or propylene oxide, to polyalkylene polyamines such as diethylenetn'amine or triethylenetetramine; adducts from polyamines such as diethylenetriamine or triethylenetetramine in excess and polyepoxides such as bisphenol-A polyglycidyl ethers; ketimines, for example from acetone or methyl ethyl ketone and bis(p-aminophenyl)methane; adducts from monophenols or polyphenols and polyamines; polyamides, especially those from aliphatic polyamines such as diethylenetriamine or triethylenetetramine and dimerised or trimerised unsaturated fatty acids, such as dimerised linseed oil fatty acid (Versamid); polymeric polysulphide ("I'hiokol); dicyandiamide, and aniline-formaldehyde resins; polyhydric phenols, for example resorcinol, 2,2-bis(4-hydroxyphenyl) propane or phenol-formaldehyde resins; boron trifluoride and its complexes with organic compounds such as BF ether complexes and BF -amine complexes, for example BF -monoethylamine complex; acetoacetanilide-BF complex; phosphoric acid; triphenylphosphite; polybasic carboxylic acids and their anhydrides, for example phthalic anhydride, A4-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,6-endomethylene A tetrahydrophthalic anhydride, methyl-3,6-endomethylene A tetrahydrophthalic anhydride (=methylnadicanhydride), 3,4,5,6,7,7-hexachlor- 3,6-endomethylene A tetrahydrop'hthalic anhydride, succinic anhydride, adipic anhydride, azelaic anhydride, sebacic anhydride, maleic anhydride, dodecenyl-succinic anhydride; pyromellitic acid diam-hydride or mixtures of such anhydrides.

It is furthermore possible to employ curing accelerators in the cure, and in particular when using polyamides, polymeric polysulphides or polycarboxylic acid anhydrides as curing agents; such accelerators are for example: tertiary amines, their salts or quaternary ammonium compounds, for example 2,4,6-tris(dimethylaminomethyl) phenol, benzyldimethylamine, 2-ethyl-4-methyl-imidazole, and triamylammonium phenolate; or alkali metal alcoholates such as for example sodium hexanetriolate.

The expression curing, as used here, relates to the conversion of the above-mentioned diepoxides into insoluble and infusible cross-linked products and in fact as a rule with simultaneous shaping to give shaped articles such as castings, pressings or laminates or to give twodimensional articles such as coatings, lacquer films or adhesive bonds.

Corresponding to the choice of the formation component of the polyglycidyl ester (I) as well as of the type of curing agent, highly flexible or slightly flexible or rubbet-elastic articles are accordingly obtained. The shaped articles in general show a low water absorption, good notched strength, high tensile strength and high elongation at break. The technical products of low chlorine content of about 0.5% are furthermore distinguished by particularly advantageous corrosion behaviour (for example when used for embedding or cementing metallic conductors).

If desired, active diluents such as for example styrene oxide, butyl glycidyl ether, isooctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether and glycidyl esters of synthetic highly branched mainly tertiaryaliphatic monocarboxylic acids (Cardura E), or cycloaliphatic monoepoxides such as 3-vinyl-2,4-dioxaspiro(5,5)-9,10-epoxyundecane can be added to the diepoxides according to the invention in order to lower the viscosity.

The diepoxides according to the invention can furthermore be used as mixtures with other curable diepoxide or polyepoxide compounds. As such there may for example be mentioned: polyglycidyl ethers or polyhydric alcohols such as 1,4-butanediol, polyethylene glycols, polypropylene glycols or 2,2-bis(4'-hydroxycyclohexyl) propane; polyglycidyl ethers of polyhydric phenols such as 2,2-bis-(4'-hydroxyphenyl)propane (:bisphenol A), 2,2(4-hydroxy-3',5-dibromophenyl)propane, bis(4 hydroxyphenyl)-sulphone, 1,1,2,2 tetrakis(4'-hydroxyphenyl)ethane or condensation products of formaldehyde with phenols manufactured in an acid medium, such as phenol novolacs or cresol novolacs; polyglycidyl esters of polycarboxylic acids such as for example phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester or hexahydrophalic acid diglycidyl ester; triglycidyl isocyanurate, N,N' diglycidyl-5,S-dimethylhydantoin, and aminopolyepoxides such as are obtained by dehydrohalogenation of the reaction products of epihalogenohydrin and primary or secondary amines such as aniline or 4,4- diaminodiphenylmethane; furthermore, alicyclic compounds containing several epoxide groups, such as vinylcyclohexenediepoxide, dicyclopentadiene diepoxide, ethylene glycol-bis-(3,4-epoxytetrahydrodicyclopentadien 8- yI) ether, (3,4-epoxycyclohexylmethyl)-3,4-epoxycyclohexanecarboxylate, (3',4'-epoxy 6' methylcyclohexylmethyl)-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (cyclopentyl)-ether diepoxide or 3-(3',4'-epoxycyclohexyl )-2,4-dioxaspiro- 5,5 -9, 1 O-epoxyundecane.

Curable mixtures which are suitable for the manufacture of shaped articles including two-dimensional structures and which contain the polyepoxides according to the invention, optionally together with other diepoxide or polyepoxide compounds and furthermore curing agents for epoxide resins such as polyamines or polycarboxylic acid anhydrides are therefore also a subject of the present invention.

The polyglycidyl esters according to the invention or their mixtures with other polyepoxide compounds and/or curing agents can furthermore, in any stage before curing, be mixed with the usual modifiers such as extenders, fillers and reinforcing agents, pigments, dyestuffs, organic solvents, plasticisers, levelling agents, agents which confer thixotropy, flame-inhibiting substances or mould release agents.

The following may for example be mentioned as extenders, reinforcing agents, fillers and pigments which can be employed in the curable mixtures according to the invention: anthracite tar, bitumen, glass fibres, boron fibres, carbon fibres, cellulose, polyethylene powder, polypropylene powder, mica, asbestos, quartz powder, slate powder, aluminium trihydrate, chalk powder, gypsum, antimony trioxide, bentones, silica aerogel (Aerosil), lithopone, barytes, titanium dioxide, carbon black, graphite, iron oxide or metal powder such as aluminium powder or iron powder.

The following are for example suitable as organic solvents for the modification of the curable mixtures: toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone, diacetone-alcohol, ethylene glycol monomethyl ether, monoethyl ether and monobutyl ether.

Dibutyl, dioctyl and dinonyl phthalate, tricresyl phosphate, trixylenyl phosphate and also polypropylene glycols can for example be employed as plasticisers for modifying the curable mixtures.

Particularly for use in the lacquer field, the new polyglycidyl esters can furthermore be partially or completely esterified in a known manner with carboxylic acids such as especially higher unsaturated fatty acids. It is furthermore possible to add other curable synthetic resins, for example phenoplastics or aminoplastics, to such lacquer formulations.

The curable mixtures can, in the unfilled or filled state, optionally in the form of solutions or emulsions, serve as laminating resins, paints, lacquers, dipping resins, impregnating resins, casting resins, pressing compositions,

sinter powders, spreading and filling compositions, floor covering compositions, embedding and insulating compositions for electro'technology, and adhesives, as well as for the manufacture of such products.

In the examples which follow the parts denote parts by weight and the percentages denote percentages by weight;

EXAMPLE 1 (a) Manufacture of the partial ester 616 g. (4 mols) of hexahydrophthalic anhydride and 850 g. (2 mols) of polypropylene glycol having an average molecular weight of 425 and 4.7 equivalents of hydroxyl groups/ kg. were initially introduced into a suitable reaction vessel and warmed to 130 C. whilst stirring. A slightly exothermic reaction set in. After 60 minutes at 130 C. and a further 30 minutes at 140 C. the mixture was cooled to 90 C. and a sample was titrated to determine the acid content. The titration showed 2.75 equivalents/kg. of free acid groups (theory: 2.73 equivalent/ kg.), which is equivalent to practically quantitative forma tion of the half-ester.

(b) Glycidylation of the partial ester The half-ester was mixed with 2220 g. (24 mols) of epichlorhydrin in the same reaction vessel and the temperature was kept at 90 C. 20 g. of a 50% strength aqueous solution of tetramethylammonium chloride were added and this initiated an exothermic but easily controllable reaction. The temperature was kept at between 88 and 92 C. and the course of the reaction was monitored by means of a pH-electrode. The pH measuring device initially showed a value of between 5 and 7 which slowly increased and was about 2 pH units higher after about 20 minutes. After 20 to 25 minutes the reading on the pH measuring instrument rose abruptly in about 2 minutes by about 2 pH units, and this signified the end of the addition reaction. The pH electrode was removed and a dropping funnel containing 400 g. (5 mols) of aqueous 50% strength sodium hydroxide solution was attached. The reaction mixture was cooled to 55 C. and a further 20 g. of aqueous 50% strength solution of tetramethylammonium chloride were added. The apparatus was subjected to a vacuum and the sodium hydroxide solution was allowed to run in continuously over the course of 80 to 120 minutes at 70 to 100 mm. Hg and at an internal temperature of 52 to 58 C., with the water introduced and the water formed being azeotropically distilled off with epichlorhydrin. The epichlorhydrin was separated from the water in a water separator and continuously returned to the reaction mixture. A total of 300 ml. of water was separated off.

For working up, the apparatus was vented and the reaction mixture was successively washed in the separating funnel with 1000 ml. of water, 700 ml. of aqueous 5% strength monosodium phosphate solution and 700 ml. of water whilst warm. The epichlorhydrin solution is very concentrated (45% solids content) and can therefore in isolated cases form stable emulsions on washing. It was possible to destroy such emulsions by adding 100 to 250 ml. of ethanol. The epichlorhydrin solution was concen trated in a rotary evaporator under a water-jet vacuum. The residue was dried for 45 minutes at 120 C. under a vacuum of about 1 mm. Hg and then filtered through a pressure filter with Hyfio and filter paper. 1653 g. (97.8% of theory) of a pale yellow clear liquid non-crystallising product were obtained. The analytical values were:

Epoxide content: 2.3 equivalents/kg. (97.4% of theory) Chlorine content: 0.4% Viscosity (at 25 C.): 1500 cp. (Hoeppler viscometer) The product mainly consisted of the following compound The partial ester from 2'rnols of hexahydrophthalic' anhydride and 1 mol of polypropylene glycol of average molecular weight 1025 was manufactured inan analogous manner to that described in Example 1 and the diglycidyl ester was obtained therefrom in the same manner as in Example 1. The following amounts were employed for this purpose: 1025 g. (1 mol) of poly-propylene glycol of average molecular weightl025 and having 1.95 equiva} lents of hydroxyl groups/kg, 308 g. (2 mols) of hexahyf drophthalic anhydride, 2221 g. (24 mols)" of epichlorhydrin, 200 g. (2% mols) of aqueous sodium hydroxide 'solution 5 0% strength) and 2x 20 g. of tetramethylam'mo-Q nium chloride solution, 50% strength in water. 1400 g. (96.9% of theory) of light yellow, clear, liquid non-crys-f tallising product giving the following analytical values" were thereby obtained: v Epoxide content: 1.35 equivalents/kg. (97.8% of .theory) Chlorine content: 0.37% Viscosity (at 25 C.): 820 cp. (Hoeppler viscometer)v 9 The product mainly consists of the'following corn pound: e

H y -o- :on cn.-o: o

o LAH. .l. t n=about 17.5 (average 'value) EXAMPLE 3 The partial ester was manufactured from 2 mols of hexahydrophthalic anhydride and 111101 of poly-tetramethylene ether glycol (polybutylene glycol) of avearge molecular weight 1000, in an analogous manner to that described in Example 1, and the diglycidyl ester was ob'- tained therefrom in the same'manner as in Example 1. The following quantities wereused for this purpose 1000 g. (1 mol) of poly-tetramethyl'ene ether glycol (commercial product of Quaker Oats Co, obtainable under the registered name Polymeg 1000), average molecular weight 100032.02 equivalents of 'hydroxyl groups per kg.; 308 g. (2 mols) of hexa liydrophth'alic, anhydride, 2221 g. (24 mols) of epichlorhydrin, 200 g. (2 /2 mols) of aqueous sodium hydroxide solution (50% strength) and2 20 g. of tetrarnethylammonium chloride solution, 50% strength in water. p v

1366 g. (96.2% of theory) of pale yellowf clear liquid noncrystallising product were thereby 'obtained, giving the following analytical values:

Epoxide content: 1.4, equivalents/kg. (99.4%, of theory) Chlorine content: 0.2-%.-

Visocsity (at 25 C.): 1400 cp. (Hoeppler viscometer) The product mainly consists of the following compoundz-- r n=about 13.6 (average value) EXAMPLE 4 The partial ester was manufactured from 2 mols of Viscosity (at 25 C.): 1100 cp. (Hoeppler viscometer) The product mainly consists of the following compound:

hexahydrophthalic anhydride and 1 mol of poly-hexamethylene ether glycol (polyhexanediol) of average molecular weight 1250 in an analogous manner to that described in Example 1, and the ester was glycidylated in the same manner as in Example 1, The following quantities were employed for this purpose: 1250 g. (1 mol) of poly-hexamethylene ether glycol of average molecular weight 1250 and having 1.6 equivalents of hydroxyl groups per kg., manufactured from 1,6-hexanediol in the usual manner, 308 g. (2 mols) of hexahydrophthalic anhydride, 2221 g. (24 mols) of epichlorhydrin, 200 g. (2% mols) of aqueous sodium hydroxide solution (50% strength) and 2X g. of tetramethylammonium chloride solution, 50% strength in water. 1642 g. (98.3% of theory) of light yellow clear liquid product were thereby obtained, and this crystallised on cooling to room temperature and solidified to a light brown waxlike mass. The analytical values are:

Epoxide content: 1.2 equivalents/kg, (100% of theory) Chlorine content: 0.4%

Crystal transition temperature, measured in a differential calorimeter: 42 C.

The product mainly consists of the following compound:

ll L J n=about 12 (average value) EXAMPLE 5 The partial ester was manufactured from 2 mols of A -tetrahydrophthalic anhydride and 1 mol of polypropylene glycol of average molecular weight 2000 in an analogous manner to that described in Example 1 and the diglycidyl ester was obtained therefrom in the same manner as in Example 1. The following quantities were Epoxide content: 0.8 equivalent/kg. (96.6% of theory) Chlorine content: 0.'2%

1. Lin. J.

n=about 34.2 (average value).

EXAMPLE 6 The partial ester was manufactured from 2 mols of 4- methyl-A -tetrahydrophthalic anhydride and 1 mol of polyethylene glycol of average molecular weight 1450 in an analogous manner to that described in Example 1 and the diglycidyl ester was obtained therefrom in the same manner as in Example 1. The following quantities were employed for this purpose: 1450 g. (1 mol) of polyethylene glycol of average molecular weight 1450 (commercial product of Union Carbide obtainable under the registered name Carbowax 1540)--the material was dried for 4 hours at 140 C. under a high vacuum before use and then had 1.38 equivalents of hydroxyl groups/kg; 332 g. (2 mols) of 4-methyl-A -tetrahydrophthalic anhydride (technical isomer mixture), 2400 g. (26 mols) of epichlorhydrin, 200 g. (2% mols) of aqueous sodium hydroxide solution strength) and 2X25 g. of tetramethylammonium chloride solution, 50% strength in Water.

Since the end product is partially soluble in water, the working up of the reaction mixture after completion of addition of the sodium hydroxide solution was not effected as in Example 1 and instead the reaction mixture was cooled to 20 C. and filtered in order to remove the sodium chloride formed during the reaction. The filtrate was concentrated under a water-pump vacuum. The residue was dried for 45 minutes under a vacuum of about 1 mm. Hg at 120 C. and was filtered warm through a pressure filter with Hyflo and filter paper. 1824 g. (96.3% of theory) of light yellow clear resin were obtained, which crystallised at room temperature and solidified to a soft wax-like light brown mass giving the following analytical values: Epoxide content: 1.0 equivalents/kg. (94.7% of theory) Chlorine content: 0.4%

Viscosity (at 25 0.): 2100 cp. (Hoeppler viscometer).

Substance crystallises after a short time The product mainly consists of the isomer mixture of the following compounds which are positional isomers (the methyl groups can be in the 4-position or S-position relative to the glycidyl ester groups on the ring).

'11 1'2 OatsCoaobtainable under theyregisterediname Polymeg 1": 9 .3568- 1 1 18) of methyl-3,6;endomethylene-A tetrahydrophthalicanhydrid'e' (isomer 'mixture); 220g. The partlal ester was manufactured from 2 mols of (24 111015) of epichlorhydrin, 200 g, (2% 1 1013) of aquel maleic anhydride and1 mol Of poly-tetram'ethylene' ether 011s sodium hydroxide solution (50% strength) and 2 x20 5 glycol (P y y y of average molecular of mtm thyhmm nim hl idel ti 50% I weight 1000 in an analogous manner to that described strength in water; p in Example 1 and the glycidyl ester was obtained there- 1377, g 93 g% of theory) of light brown clear 1 i "from in the same manner as in Example 1. The follownon-crystallising product were thereby obtained, giving the: g quantities Were herein employed! 1000 of following analytical values: 5 p yg gghylegehether glycol of average molecular weig t 1 an aving 2.02 equivalents of hydroxyl gigg 2322:1 2: g (954% Si thepry) groups per kg. (commercial product of Quaker Oats Co. c (Ho 1 a t obtainable under the registeredgname Polymeg1000),'196 lscosl y (a epp er vlscome er) g. (2 mols) of maleic. anhydride, 2035 g. (22 mols):.of The product mainly consists of the isomer mixture of epichlorhydrin, 200 g. (2 /2 mols) of aqueous sodium the following compounds which are positional isomers, it hydroxide solution (50% streng h) and 2X g. of tetrabeing possible herein for the methyl groups to be in the methylammonium chloride solution, 50% strength in 3-position, 6-position or 7-position of the bicyclic nucleus: water. a

rn=about 13.6 (average value) 1167 g. (89.2% of theory) of light brown liquid nonf- EXAMPLE 8 cfnystallising product were thereby' obtained, giving the ollowing analytical values: I

The partial ester was manufactured from 2 mols of 3,4,5,6,7,7-hexachlor 3,6 endomethylene-A -tetrahydro- Epoxide content: 1.25 equivalents/kg. (81.8% of theory) phthalic anhydride and 1 mol of polypropylene glycol of Chlorine content: 2.2% average molecular weight 425 in an analogous manner Viscosity (at 25 C.): 7500 cp. (Hoeppler viscometer) to that described in Example 1 and the diglycidyl ester was obtained therefrom in the same manner as in Example 40 The p t is n t Stable and t t peratures above 1. The following quantities were employed: 425 g. (1 100 C. a volatile compound is eliminated which can be mol) of polypropylene glycol of average molecular weight distilled in Vacllo, e epoxide content at the same;

425 and having 4.70. equivalents of hydroxyl groups/kg, time, dropping slowly. The ep c y Was fore 742 g. (2 mols) of 3,4,5,6,7,7-hexachlor-3,fi-endomethyldistilled oflf under a highLVacuum. and at a temperature ene-M-tetrahydrophthalic anhydride, 1850 g. (20 mols) below 95 C. The product mainly consists of the folof epichlorhydrin, 200 g. (2 /2 mols) of aqueous sodium lowing compound: v I

hydroxide solution strength) and 2X 15 g. of n=about 13.6 (average value) sztrtgrilethylamm omum chloride solution, 50% strength in EXAMPLE 10 N i 1259 g. (98.5% of theory) of clear highly viscous liquid The partial ester was manufactured from 2 mols of resin having an intense dark brown colour were thereby Sueclnie fanhydride and 1 II101 of p yp py glycol obtained, giving the following analytical values: of average molecular weight 1025 in an analogous manner to that described in Example 1 and the ester was Epoxide content. 1.2 equivalents/kg. (76.7% of theory) glycidylated in the same manner as in Example I. The

Chlorine content: 33.6% (101% of theory) f o ollowrng quantities were employed for this purpose: 1025 vlscoslty (at 25 30,000 p. oeppler-vls g."(1 mol) of polypropylene glycol of average molecular The product mainly consists of the following comweight 1025 and having 1.95 equivalents of hydroxyl pound:

n===about 7(average value) groups per kg., 200 g. (2 mols) of. succinic .anhydride.

1850 g. mols) of epichlorhydrin, 200 g. (2% mols) anhydride containing 0.515 equivalents of free acid of aqueous sodium hydroxide solution (50% strength) groups per kg. and having a calculated anhydride group and 2X 17 g..of tetramethyl-ammonium chloride solucontent of 5.15 equivalents/kg, 2775 g. mols) of tion,.50% strength in water. I epichlorhydrin, 216 g. (2.7 mols) of aqueous sodium 1330 g. (99.5% of theory) of light yellow, clear, liquid hydroxide solution (50% strength) and 2x 25 g. of non-erystallising product were thereby obtained, giving 5 tetramethylammonium chloride solution, 50% strength in the following analytical values: 1 water.

1694 g. (96.2% of theory) of pale yellow clear liquid Epoxlfle content: equlvalentS/kg' (835% of theory) product were obtained, which on cooling crystallised and Chlorine content: 1.95%

l'd'fi t l' h -lk l t' Viscosity (at 25 C.): 410 cp. (Hoeppler viscometer) 10 ig t s z lg t gTey Wax 1 e mass The am y lcal The product mainly consists of the following com- Epoxide content: 1.2 equivalents/kg. (96% of the calpound: culated value) EXAMPLE 11 The product contains 1.5 to 2% of sebacic acid diglycidyl ester, with the remainder consisting mainly of the The partial ester was manufactured from 2 mols of following compound:

glutaric acid anhydride and 1 mol of polyethylene glycol n=about 12 (average value) of avera e molecular wei ht 1450 in an analo ous manner to tfiat describedin Example 1 and this ester was EXAMPLE 13 glycidylated in the same manner as in Example 1. The The partial ester was manufactured from 2 mols of following quantities were employed for this purpose: 3 alkyl 6 alkylenecarboxy A tetrahydrophthalic 1450 g. (1 mol.) of polyethylene glycol of average anhydride (Admerginat A of Brinckman & Mergell molecular weight 1450 (commercial product of Union GmbH.) and 1 mol of polypropylene glycol of average Carbide obtainable under the registered name Carbowax molecular ig 0, in an analogous manner to that 1540) ih m t rial wa dri d for 4 hour t 140 C, described in Example 1, and the tetraglycidyl ester was under a, high vacuum before use and then had 138 obtained therefrom in the same manner as in Example 1. equivalents of hydroxyl groups per kg; 228 g. (2 mols) of glutaric acid anhydride, 2775 g. (30 mols) of epichlor- C OOH hydrin, 200 g. (2% mols) of aqueous sodium hydroxide 0 solution (50% strength) and 2X 25 g. of tetramethyl- U H ammonium chloride solution, 50% strength in water.

Since the end product is partially soluble in water, the O C CH working up of the reaction mixture after completion of ([311 gm the addition of the sodium hydroxide was not effected as C fi in Example 1 but as in Example 6. 1710 g. (92.5% of g theory) of pale yellow clear liquid product were obtained, H CH and this crystallised at room temperature to give a white 3 wax-like mass. The product gave the following analytical values: Admerginat A, a mixture of two isomeric compounds Epoxide content: 1.05 equivalents/kg. (94% of theory) C H O (M=378.5)

Chlorine content: 05% The following quantities were employed: 600 g. (1 mol) The product mainly consists of the following comof polyethylene glycol of average molecular weight 600 pound: (product of Union Carbide obtainable under the regisn=about 32.5 (average value). tered name Carbowax 600)the material was dried for 4 hours at 140 C. under a high vacuum before use and EXAMPLE 12 5 then had 3.35 equivalents of hydroxyl groups per kg.; .The partial ester was manufactured from polysebaclc 870 g. of Admerginat A having an anhydride conten acid anhydride and polyhexamethylene ether glycol of 2.3 equivalents/kg. (87% of theory) and a saponifica- (polyhexanediol) of average molecular weight 1250 in an tion number of 407 (91,5 of theory), 2400 g, (26 mols) analogous manner to that described in Example 1 a of epichlorhydrin, 430 g. (5.375 mols) of aqueous sodium glycidylated in the same manner as in Example 1. The hydroxide solution (50% strength) and 2X25 g. of tetrafollowing quantities were employed for this purpose: methylammonium chloride solution, 50% strength in 1250 g. (1 mol) of polyhexamethylene ether glycol of ater,

average molecular Weight 1250 and having quiva- The working up of the reaction mixture after complelents of hydroxyl groups per kg., manufactured from 1,6- tion of the addition of the sodium hydroxide solution was hexanediol in the usual manner, 388 g. of polysebacic acid not effected as in Example 1 but as in Example '6. 1690 g.

(98.7% of theory) of light clear brownish-red liquid noncrystallising product were obtained. The analytical results were:

Epoxide content: 2.2 equivalents/kg. (93.2% of theory) Chlorine content: 0.3% Viscosity (at C.): 7900 cp. (Hoeppler viscometer) The product mainly consists of a mixture of isomeric compounds, for example of O C QCH-CHr-O-PJ n=about 13.2 (average) 2)lorl H cH AH as v (5H9...)

cnr-cn-cmostrength according to DIN and the elongation at break were determined.

Glycidyl ester according to Example No 1 1 2 Parts by weight of glycidyl ester 100 100 24 Parts by weight of epoxide resin 0 Parts by weight of hexahydrophthalic anhydride" Parts by weight of benzyldiinetlzlylamlne- 0. 2 0. 2 15 Parts by weight of quartz 0 0 0 '0 0 Tensile strength according to DIN 0. 9 6. 4 6. 0 2. 6 0. r

Elongation at break, percent- Toughness: %Xtensile strengthX Appearance after cure Water absorption in percent, 4 day Water absorption in percent, 1 hour at 100' s at room Ctemperature 1 Clear yellow. 7 Opaque grey. a Opaque white.

- E .PLE 14 "Glycidyle'ster Some of the polyglycidyl esters manufactured accords xfiilit fio 1 ing to Examples 1-13 were mixed together with a llqllld 45 cycloaliphatic epoxide resin A which had an epoxide con- 33: E; g? gg'i gf z g g -"f g tent of 6.2 equivalents/kg, and an accelerator B which Pzgtsd by weight of hexahydrophthalicanhyv 1 colksisted of approxlmafely Strength 801mm 9 Par t s i'y'argre35555565655555;"";: 25 0.25 sodlum metal in hexanetrrol, as with hexahydrophthalic {Iarts bydwellght oi flglacrlgz powder 2% 20g 18 88S re V8. 85 l acld anhydnde Wlth genfl? F Q to 3 Q Tensiie stren ch :ccordlngto DI 1.2 2.5 neous melt, and were cast in silrcomsed 4 mm. tensile rod gog a iou at b p nt- 28 20 moulds according to DIN 53,455. The samples were cured 17 25 o 0 @CW o o Epoxide Resin A Glycldyl ester according to Example No.--..

Parts by weight of glycidyl estcr Parts by weight of epoxide resin A Pigt sd by weight of hexahydrophth n e Parts by weight of accelerator B.-. Tensile strength according to DIN, kgJmm Elongation at break, percent "Toughness" kiXtensile strengthxelongation at break Appearance after curem E0! mom m w 2K1 mama A go 800 Opaque white.

' EXAMPLE 15 Some of the polyglycidyl esters manufactured according to Examples 1-13 were mixed, by themselves or to- EXAMPLE 16 Some of the polyglyc'idyl'esters manufactured according to Examples 1-13 were homogeneously mixed-with triethylene tetrarnine, together with the epoxide resin C described in Example 15, without warming, and were,cast in siliconised 4 mm. tensile rod mouldsaccording to DIN 53,455. After 3 days at room temperature the tensile strength according to DIN and the elongation at breakwere determined; 1 I 1:

Glycldyl ester according to Example No Parts by weight of glycldyl ester ,p Parts by weight of epoxide resin 0... Parts by weight of triethylene tetramine .5... I Tensile strength according to DIN. kgJmmJ--.

Elongation at break. percent Toughness: xtenslle strengthxel at EXAMPLE i7 Epoxide resin D: by way of comparison, the partial; ester was manufactured from 2 mols of hexahydrophthalic anhydride and 1 mol of ethylene glycol in an analogous 17 18 manner to Example 1, and the diglycidyl ester (epoxide We claim: resin D) obtained therefrom in the same manner as in 1. A polyglycidyl ester of formula [CH CHCHr-OC R CO-A-O-CRz CO-CHg'CH-CHg] O M t t LL25 Example 1. The yield was 91% of theory; the product wherein R and R each represent a residue, obtained by had the following analytical values: removal of the carboxyl groups, of an aliphatic or cycloaliphatic polycarboxylic acid having 2 to 4 carboxyl Total chlorine content: 1.0% (according to Wurzschmitt) 322, 8 g sggi gz gs gi g ggi zigigii a i -Zia: vlscoslty' (at 9700 (Hoeppler vlscometer) age molecular weight of at least 200, and wherein m and Epoxide resm E: the partlal ester Was mauufa fl n are integers having a value of at least 1 and at most 3. from 2 mols of M-tetrahydrophthahc anhydride and 1 2, A olyglycidyl st r of f rmula Epoxide content: 4.0 equivalents/kg. (96% of theory) mol of ethylene gly l in all allalflgolls manner to h wherein R and R each represents a residue, obtained by desfirlbed 111 pl 1 and the Y 3/ ester p removal of the carboxyl groups, of an aliphatic or cycloresin E) was obtain d the 111 the Same manner aliphatic polycarboxylic acid having 2 to 4 carboxyl as in Example 1. The yield was 94% of theory; the prodr t th 'd b not had the followmg analytlc a1 values: groups A epresen s e resl ue o tamed by removal of the two hydroxyl groups, of a polyalkylene glycol of aver- Epoxide content: 4.1 equivalents/kg. (98% of theory) age molecular Wtfight of at least and wherein m and Total chlorine cont nt; 10% (according t W n are integer having a value of at least 1 and at most 2.

schmitt) 3O 3. A diglycidyl ester of formula Viscosity (at 25 C.): 15000 cp. (Hoeppler viscometer) The epoxide resins D and E manufactured according to wherein R represents an unsubstituted or alkyl substi- Example 17 were cast and cured in accordance with Extuted cyclohexylene or cyclohexenylene residue and A repample 15. 4O resents a residue, obtained by removal of the two hydroxyl groups, of a polyalkylene glycol of formula Glycidyl ester according to Example 17 D D E E D Parts by weight ofglycldyl ester 100 50 100 50 50 I- I Parts by weight of epoxide resin 0 50 50 50 HO-Alkylene-O Alkylene-OH Parts by weight of hexahydrophthalic anh L J;

dllde 63 72 71 llzarts gy weigllilt otgbenzyldimeghylamin 0.2 0.2 ar 8 W81 0 uar Z 0W 8! u n Tensile s trength acdbrding o DIN.kg./mm. 4.2 0.0 5.0 0.5 6.0 Wherem Alkylene 18 an alkylene ,resldue having 2 to 6 Elongation at break. percent 4 3 3.5 3 2 carbon atoms and the number x 15 so chosen that the i iifi. ili ffi fffffffi i flii ilfifiil 9 8.8 9.8 6.0 average molecular Weight of the Polyalkylene glycol is 250 Water absorption in percent, 4 days at room 2 t0 2500.

temperature" 4. Diglycidyl ester of formula I I /CH; d-o-am-on-om CH2-oH-oH2-od\ 052 OH; HO (1H2 5H1 /Cg /CH2 ofiz ("JO CH-CH O on, 0 L5H: L Il=435 0 The polyglycidyl esters according to the invention show 5. Diglycidyl ester of formula l ll CH2 d-o-om-om-om CH OH-CHz0-C\ CH2 0 2 HO Ofi CH2 s is CH2 CO|-CH-CH2O o Cfiz a higher elongation at break and greater toughness than the diglycidyl esters manufactured in Example 17. 75

8. Diglycidyl ester of formula 9. Diglycidyl ester of formula where z=2 to 8 and n=4-35.

10. Diglycidyl ester of formula wherein 2:2 to 8 and n=1333.

11. Diglycidyl ester of formula o gLIgL JH L .I- u

wherein z=3 to 8 and n=6 to 20.

NORMA S. MILESTONE, Primary Examiner US. Cl. X.R.

260-2 EC, 2 EA, 2 N; 260-468 B, 468 R, 485 G 253 3 UNITED STATES PATENT OFFICE,

CERTIFICATE OF CORRECTION Patent No. 3,651,098 D d March 21, 1972 Inve t r( ALFRED HEER ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line A, after "assignors to" delete 'Ciba Limited" and insert ClBA-GEIGY AG Column 18, the extreme right side of the formula following -CHCH2 Column 19, the bottom of the formula of claim 8 -ECHCH -O} should read {CH-CH -O] --3 n I n CH3 delete "n=4-l5" and insert n= L-35 -5 line 30, "-CH- CH" should read the center of the formula of claim 9 ('lH-CH -O should read (|3HCH 0 Signed and sealed this 25th day of June 197A.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. C. MARSHALL DANN Commissioner of Patents Attesting Officer 

